Process of shrinkproofing wool with epoxy carbamates and a polyamine

ABSTRACT

THIS INVENTION CONCERNS NOVEL EPOXYALKYL CARBAMATES OF THE STRUCTURE:   R-(NH-CO-A-CH&lt;(-O-CH(-D)-))2   WHEREIN   WHERE E IS ARYLENE), AND (B) HYDROCARBON RADICALS. THE COMPOSITIONS OF THIS INVENTION ARE USEFUL FOR THE DIMENSIONAL STABILIZATION OF PROTEINACEOUS SUBSTRATES SUCH AS WOOL.   -E-NH-CO-   A IS A DIVALENT ALKYLENE RADICAL SELECTED FROM THE GROUP CONSISTING OF STRAIGHT-CHAIN ALKYLENE RADICALS AND BRANCHED-CHAIN ALKYLENE RADICALS, D IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL RADICALS, AND R IS DIVALENT ORGANIC RADICAL OF AT LEAST 12 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF (A) LINEAR POLYMERS TERMINATED ON BOTH ENDS OF ARYLENECARBAMOYL RADICALS

"United States Patent Oflice 3,684,429

Patented Aug. 15, 1972 atoms, are useful as dimensional stabilizers for proteina- 3,684,429 ceous substrate such as wool. PROCESS OF SHRINKPROOFING WOOL H Proteinaceous fibers as exemplified by wool have several EPOXY CARBAMATES AND A POLYAMINE advantageous properties which make them valuable in Giuliana C. Tesoro, Dobbs Ferry, N.Y., and Wing K81 5 article or garment fabrication. These properties include g f fi g ffi' k to Stevens & good thermal insulation, good resilience, vfit, durability, No 62 g a May 22 1967 Sen No. wrinkle resistance and good receptivity to dyeing. Un-

640,397, bi id n this application 5 1970, fortunately, the untreated wool fibers and fabrics manu- Ser. No. 26,451 factured from wool are rather sensitive to extended con- Int. Cl. D06m 13/38 10 tact with water such as is experienced during normal US. Cl. 8127.6 11 Claims laundering procedures. As a result of exposure to water,

woolen textiles shrink and felt, and their use for certain textile applications has been severely restricted. ABSTRACT OF THE DISCLOSURE Within recent years a major amount of research has This invention concerns novel epoxyalkyl carbamates 15 n undertaken to P the dimenslonal f y fi of the structure: wool and other proteinaceous substrates. Desirably, d1- mensional stabilizers in addition to performing their prime r E function of shrinkproofing, would be inexpensive to apply,

R NH CAGE-CH) could be applied by non-technically trained labor, using L 0 conventional textile treating equipment and the treated wherein fiber or fabric would be resistant to repeated normal launderings. The development of reagents possessing this combination of properties would represent a useful advance in the art.

It is an object of this invention, among others, to prepare novel products useful in improving the dimensional stability of proteinaceous fibers and fabrics such as wool.

Another object of this invention is the preparation of homopolymers and copolymers of the above epoxide products which are useful as coatings and finishing agents.

Additional objects will become apparent to those skilled 0 in the art after a perusal of this application. l In practice, a divalent organic diisocyanate reactant whose generic formula can be represented by: where E is arylene), and (b) hydrocarbon radicals.

The compositions of this invention are useful for the Wherem dimensional stabilization of proteinaceous substrates such R i d fi d as described i f is contacted with an epoxy. as WOOL alkanol generically represented as:

HOAHC\ CH-D The present application is a divisional of application 0 Ser. No. 640,397, filed May 22, 1967, now abandoned. wherein This invention relates to novel polyfunctional epoxides useful as finishing agents and as intermediates for prepar- 4 ing finishing agents.

A is a divalent alkylene radical selected from the group consisting of straight-chain alkylene radicals and branched-chain alkylene radicals, 25

D is selected from the group consisting of hydrogen and alkyl radicals, and.

R is a divalent organic radical of at least 12 carbon atoms selected from the group consisting of (a) linear polymers terminated on both ends of arylenecarbamoyl radicals A is a divalent alkylene radical selected from straightchain and branched chain alkylene radicals containing More particularly this invention concerns novel epoxyf-rom l to 8 carbon atoms alkyl carbamates the structure D 18 selected from the group consisting of hydrogen and monovalent alkyl radicals of from 1 to '8 carbon atoms, I" under reaction conditions (time, temperature, pressure, R- NH(JJQACH CH. D solvents, ratio of reactants, etc.) suflicient to produce L 2 the afore-defined epoxy products of this invention, and

isolating the products contained therein. wherein Th dii c n t r cta A is a divalent alkylene radical selected from the group i li sg in ieil 1:; thz st fic t iii'e i can be gen consisting of straight-chain alkylene radicals and branched-chain alkylene radicals, O$N R N=O:O D is selected from the group consisting of hydrogen and wherem alkyl radicals, and R is a divalent organic radical containing at least 12 car- R is a divalent organic radical of at least 12 carbon atoms bon atoms selected from two classes of radicals:

selected from the group consisting of (a) hydrocarbon radicals, and

(a) linear polymers terminated on both ends by (b) linear polymers terminated on both ends by arylarylenecarbamoyl radicals enecarbamoyl radicals R (E-NHi J- where E is arylene), and wherein E is arylene' such as phenylene, methyl- (b) hydrocarbon radicals phenylene, and dimethylphenylene. These products, particularly those where R is The hydrocarbon radicals which comprise the first class 2 2 7 (a) are preferably aliphatic or cycloaliphatic radicals derived by polymerizing a saturated or unsaturated fat acid wherein G is a dimerized fat radical of at least 12 carbon having 8 to 24 carbon atoms. The preparation of fat acids isdisclosed in British Pat. 1,023,390, published Mar. 23, 1966. As indicated in the patent, the term fat acids includes naturally occurring or' synthetic saturates,

ethylenically unsaturated and acetylenically unsaturated acids. The term polymeric fat radical is generic to the divalent, trivalent and polyvalent radicals of dimerized, trimerized and higher polymers of fat acids. The preferred reactants are those in which the radical R is --CH GCH wherein G is a dimerized fat radical of at least 12 carbon atoms.

The second class of 'values (b) that the radical R can assume in the above formula comprises: linear polymers terminated on both ends by arylenecarbamoyl radicals O -ENH-i'2 wherein the symbol E is arylene. This class canbemore clearly expressed symbolically within the structure:

wherein E is an arylene radical, and

Z is'selected from the group consisting of:

(I) polyalkyleneoxy or polyoxyalkylenes (4II,,I-I ;,O) wherem p ranges between 3 and 6 inclusive, and n ranges between 2 and 200 inclusive,

(2) the chain of a linear polyester o...H2mo-o-1.omn,.,o-

wherein m ranges between 2 to 10 inclusive, and v ranges between 2 and 80 inclusive,

(3) the oxygen-terminated chain of a polymer of an al-kad-iene such as a chain of a polymer of 1,4-butadiene, {CI-l CHCHCH O-, wherein u ranges between 55 and 65 inclusive.

Illustrative epoxyalkanols which can be utilized as coreactants with the diisocyanates are as follows:

o v o no onlcn=cmnc-oncni o nocmn -nc -cn-onrcrn on.

' are run at atmospheric or near" atmospheric pressure although thesolvents are commonly stripped oil under reduced pressure. The reaction time varies according to the reactants employed and the temperature at which the reaction is run and therefore cannot be stated precisely. However, at temperatures of about 20-35" C. most reactions are complete within 4 to 2.4 hours. Longer times-are not harmful. v V While all of the afore-described epoxyalkyl carbamates are useful as finishing agents or as intermediates useful in preparing finishing agents, as in any large group, certain members of the group are to be preferred to the group as a whole. In'this instance, the preferred members are epoxyalkyl carbamates of theformula:

s un OAHC-GHe] v a These compounds are preferred because they form particularlyv effective finishing compositions when combined with polyamine co-treating agents such as diethylenetriamine, triethylene-tetramine, tetraethylene-pentamine and the like, in equivalent weight ratios ranging from 2:1 to 1:5. The mixtures not only are inexpensive, but give more ellicacious results than do the epoxyalkyl carbamate reagents alone.

The products are durable dimensional stabilizers for W001 and can be prepared in good yield under moderate reaction conditions from inexpensive starting materials.

To better illustrate the workings of this invention in more detail, the following preparation and application examples are submitted. In all instances, amounts shown are in parts by weight unless otherwise noted.

EXA PLE -1 Preparation of a reactive polyfunctionai epoxide produced by the addition of 2,3-epoxy-l-propanol to a diisocyanate derived from toluene diisocyanate and polytetramethylene ether glycol First Stage:

C. are ordinarily employed. Near stoichiometric propor- DESCRIPTION OF STARTING MATERIALS The polytetramethylene ether glycol used as a reactant is a commercial grade produced from tetrahydrofuran; molecular weight 10001-50 (hence n has an average value of 13.6:0J); hydroxyl number 112.5:35; waxy solid melting at 35 to40 C.

The toluene diisocyanate reactant is a commercial grade having an 20 "ratio of .2,4 and 2,6" isomers.

First stage Toluene diisocyanate (187.5 grams, 0.5 mole) is added dropwise to a stirred solution of 202 grams (0.2 mole) of polytetramethylene ether glycol in 200 grams of dichloromethane at room temperature while nitrogen is bubbled through the solution. After the addition is complete the solution is stirred at 30 C. under nitrogen for 9.5 hours. The infrared spectrum of the resulting reaction mixture is devoid of the absorption band characteristic of hydroxyl, thus indicating completion of the desired reaction.

Second stage In order to convert the isocyanate-terminated polymer to linear macromolecules terminated on both ends with epoxy groups, the reaction product described above is added slowly to 32.6 grams (0.44 mole) of 2,3-epoxy-lpropanol dissolved in 100 grams of dichloromethane at room temperature.

After completion of the addition, the reaction mixture is stirred for 5 additional hours at room temperature. Then solvent was distilled olf under reduced pressure at room temperature. The product has an oxirane content of 5.04%. (The theoretical maximum oxirane content is 5.7% for the diepoxide.)

EXAMPLE 2 Preparation of the reactive polyfunctional epoxide produced by the addition of 2,3-epoxy-1-propanol to a diisocyanate derived from dimerized C unsaturated fatty acids A commercial grade of diisocyanate obtained from dimerizing C unsaturated fatty acids described in British Pat. 1,023,390, published Mar. 23, 1966, is used as the C diisocyanate. The average value of y in the formulas shown above is approximately 66. The material has 14% -N=C'=O, less than 0.1% hydrolyzable chloride, an assay of at least 98% and a viscosity at C. of 170 centipoises. A solution consisting of 240 grams (0.4 mole) of the diisocyanate and 100 grams of benzene is added dropwise at room temperature to a stirred solution of 65 grams (0.88 mole) of 2,3-epoxy-1-propanol in 100 grams of benzene. After completion of the addition, the reaction mixture is stirred at room temperature for 5 hours, then allowed to stand at room temperature overnight. At the end of this time the solvent and excess 2,3-epoxy-lpropanol are evaporated oif at room temperature under reduced pressure to yield a product having an oxirane content of 2.65 milliequivalents per gram. (The theoretical maximum oxirane content for the reactive diepoxide is 2. 68 milliequivalents per gram.)

EXAMPLE 3 Preparation of the reactive polyfunctional epoxide produced by the addition of 2,3-epoxy-1-propanol to a diisocyanate derived from a linear polyester A solution composed of 100 grams (0.226 equivalent) of an industrial grade of an isocyanate-terminated linear polyester (having the structure given above, wherein m is about 6, and v averages between 3 and 4) and 100 grams of dichloromethane is added dropwise at room temperature to a stirred solution of 18.3 grams (0.248 mole) of 2,3-epoxy-l-propanol in 50 grams of dichloromethane. After completion of the addition, the reaction mixture was stirred at room temperature for 5 hours and the solvent and excess 2,3-epoxy-1-propanol are distilled off under reduced pressure. The product has an oxirane content of 1.83 milliequivalents per gram. (The theoretical maximum oxirane content is 1.91 milliequivalents per gram for the diepoxide.)

EXAMPLE 4 Preparation of the reactive polyfunctional epoxide produced by the addition of 2,3-epoxy-1-propanol to a diisocyanate derived from toluene diisocyanate and a polymer of butadiene First Stage:

First stage The hydroxyl-terminated polybutadiene used as starting material is a technical grade having a hydroxyl content of 0.80 milliequivalent per gram, an iodine number of 395, and an average molecular weight of 32501-250. The degree of polymerization, u ranges between 55 and inclusive.

The following procedure is used to convert the hydroxyl-terminated polybutadiene into essentially linear macromolecules terminated on both ends with isocyanate groups. A 2-liter, 3-neck flask equipped with a stirrer, a thermometer, a gas inlet tube, and a dropping funnel is charged with 200 grams of the hydroxyl-terminated polybutadiene dissolved in 200 grams of dichloromethane. Toluene diisocyanate (43.6 grams, 0.25 mole of 2,4 and 2,6 isomers in the ratio of 8/20) is added slowly while a stream of nitrogen is passed into the solution and the temperature is maintained at 20 *C. After completion of the addition, the solution is stirred at 25 to 28 C. for 8 hours.

Second stage To the above stirred solution of intermediate produced in the first stage (namely the diisocyanate derived from a polymer of 1,4-butadiene) is added dropwise a stoichiometrically suflicient quantity of 2,3-epoxy-l-propanol Contained in dichloromethane solvent to form a product corresponding to the structure below. The reaction condi-' tions and isolation procedure is comparable to that em- 8 Flex abrasion resistance-In cycles: ASTM D-l175 61T; 0.5-pound head weight and 2-pound toggle tension on Stoll Flex Abrader.

Laundering method for washable woolens.First,

ployed in Examples 1 to 3. 5 swatch was conditioned for at least 4 hours (relative hu- [{CH;CH=CHCHz}.,O-] midity at 65 :2%, 21il C.), and markmgs were appl ed 10 inches apart. Then: laundered 1n home-type machine; fi" full water level; 5-pound load; FAB or TIDE detergent; 0 15-minute wash at 40 0; running suds 1.5 to 2 inches; Q; 10 automatic rinse; dried fiat on horizontal screen; flat-bed 2 pressing at 135 to 149 C. for seconds without steam; reconditioned for at least 4 hours and re-measured. wherem the average value of u ranges between 55 and The number of cycles (as 0 1 or of laundering and 65 inclusive.

t bl nd1tdbNo.L,1L, l0 es c- The dimensional stab111z1ng agents of this invention can ag drying 1s 1 ca e y or 1 1' P6 be applied to the .pmiemaceous substrate by immber of Shrinkage in laundering in percent.- See Laundering conventional applicahon methods well known in the tcx- Method for Washable Woolens, above. file These include are not .hmited to paddmg Stiffness test resultsinmilligrams percentimeter'ASTM brushing swaying, wattng and -F D1388-55T Cantilever Method. 1 1 be in the form of solutions, slurries, suspens ons, emul- Parts and percentages were by weight, unless otherwise 510113 or the like, where appropr ate; the main requirenotei mam being that at least stabihzmg aimount of reagent Abbreviations in tables.When used individually F is deposited on the protemaceous textile substrate to be means fining direction, and W means warp direction. Note treated. A stabiiizing amount 1s that quantity of reagent the special meanings of the following 34mm abbrevia required to minimize dimensional changes from takmg tions: place in the wet-laundered proteinaceous material. Bethe Weight of the bath. The term is applied cause of experimental valuables inferences from Wa when expressing the concentration of an ingredient to reagent and the pamclllar fi sought a Swimming in the liquid mixture used for impregnating samples of amount cannot be stated with precision. However, in most fabria msiams ranges betlveen 05-10% by OWE-On the weight of fiber (or fabric), 1.5., based Welght cf reagent i the weight of treateid on the Weight of fabric prior to padding. The percentage strate the upper P 9 govenfed by PP 9 of a reagent OWF means the add-on of solids expressed siderations. Ordinarily, 1t 1s convement to utilize an inert in percent on the dry basis. solvent where solutions are employed. The choice oi s o1- pickup, Le the wet adhm {usually ex 1? 15 f d f g as {t g "g g fi presed in percentage OWlwhich is the gain from soluc aractenstlcs 1t 15 W01 0 f oge 5 tion penetrating the fabric, measured immediately after other P R Whlch couldfeact wlthfhe oxlfane l l padding. As used herein, padding consists of the dual Illustrative mert solvents mclude tertiaryhalnudes so; as process of impregnating the fabric by passing it through NsN dlmcthylforfnfimldih j dune Y a pad bath and then passing the wet fabric through methyl 2 pyrrohdmone, 1,5 d1methyl-2-pyrrol1d1none, 40 squeeze rollers or wringers cyclic ethers such as the dioxanes and trioxanes, ahphatic wh expressed in percent, the foregoing terms are ethers Such as related as follows: own) multi lied b WPU CH3OCH2CH30CH3 100%= own P Y I i and sulfoxides such as dimethyl sulfoxide. 7 EXAMPLE 5 A convenient mode of application is padding. In this procedure the textile is impregnated with a solution of the i g gzg g 2223 153 g g i 1e 2 wool reagent in inert solvent, the rolls of the padder being set shrinka g 1mm d 1 0 ex 3 Eamon Stiffness to the desired wet pickup. The treated textile is dried, g enng usually between about 40 C. to 85 C. and cured above sarflples W001 fabrlc 011E065 P Square 100 C. The cured, dried samples are usually moisture Y a Plan! Weave) fldlllflfled with the relative conditioned to the desired moisture content by exposing hufmdlty at 65i2%(21i1 and g ed On an anathem to an appropriate humidity leveL lyt1cal balance. Thesamples are padded with various con- In addition to the dimensional stabilizing reagents of F P' of the d16P0X1de of Example 2 n solvent conthis invention, the padding bath can contain one or more slstmg of toluene y am1de (1:1), with various optional textile adjuvants such as softeners, contetraethylenepentannn? 3180 Present m the percentages ditioners, surfactants and the like. Since these reagents Shown on the following table- The Wet p f p ra g are not critical to the success of this invention, no attempt 115 to 120% The samPles are odfled at 50 i0 is made to enumerate the various adjuvants that can be then Pured for 5 mmufes 135 Q Next, the employed. It will suflice to say exhaustive lists of these 60 Samples are rmsed m P-dloxane, and can be found in the technical and patent literature. thoroughly R T dned samples are condftfoned with the relative humidity at and the conditioned Evaluatl? test methods samples weighed on an analytical balance to determine Dry cleamng.-Durab1litytest: Used commercial equipweight gains. Data on both treatment and evaluation are ment formulation. in the following table:

OWB, percent N o. L., warp Shrinkage in launderlug, percent Actual Flex Tetraethylweight; abrasion 1 wash 10 washes Dlepoxide ene penta- WPU. OWF, ga resistance, Stlfiness, Sample of Ex. 2 mine percent percent percent cycles mg./cm. W F W F 9 EXAMPLE 6 Application of the diepoxide of Example 2 to wool: further variations on 'Example 5 Samples of 100% wool fabric (6.15 ounces per square yard in a plain weave) are treated similarly to those of Example 5, according to the variations evident in the following table, which includes data on both treatment and evaluation.

cal R is a hydrocarbon radical.

Flex Shrinkage in laundering, OWB, percent abrasion percent Actual resistance, Tetra- Cure weight cycles to I wash 10 washes Diepoxide ethylene- WPU, OWF, temp., gain, rupture Sample of Ex. 2 pentamlne percent percent 0. percent (W., No. L.) W F W F 7. 0. 71 114 7. 98 135 10. 3 870 None 0. 5 1. 5 1. 5 7. 0 0. 71 114 7. 98 163 10.2 825 0. 5 0. 5 1. 5 1. 5 5. 0 0.51 113 5. 65 135 8. 08 825 0. 5 0. 5 1. 5 1. 5 5.0 0.51 114 5.70 163 7.26 870 0.5 0.5 2.0 1.5 7. 0 '2. 12 122 8. 54 135 12. 0 850 0. 5 0. 5 1. 5 l. 5 7. 0 2. 12 118 8. 26 163 12.1 850 0.5 0. 5 1.5 I. 5 5.0 1. 52 120 6. 00 135 9. 02 900 0. 5 0. 5 1. 5 2. 5 5.0 1. 52 122 6. 10 163 9. 81 1, 050 0. 5 0. 5 1. 5 1. 5

EXAMPLE 7 3. The process of claim 2 wherein R, the hydrocarbon Application of the diepoxide of Example 4 to wool The product of Example 4 is applied to samples of 100% wool fabric (6.15 ounces per sq. yard in a plain weave) conditioned as in Examples 5-6. Processing and testing are identical to the aforesaid examples. Comparable improvements in the treated fabrics are obtained.

As the above examples and previous discussion indicate, the inventive compositions are advantageous in several respects. For example, the products can be prepared from available starting materials and are formed under relatively flexible reaction conditions. In addition, the products lend themselves to textile modification since they undergo their reactions, including polymerization, under relatively mild reaction conditions. This enables the novel diepoxide products to impart good dimensional stability to wool in economically feasible concentrations and the stabilized wool is durable to repeated laundering.

The metes and bounds of this invention in both its product and process aspects are best determined by reference to the claims which follow.

What is claimed is:

1. A process for dimensionally stabilizing a woolen fabric comprising applying to said fabric a solution in an inert solvent of:

(1) a stabilizing amount of an epoxyalkyl carbamate of the structure:

E is phenylene, methylphenylene or dimethylphenylene, and

(b) hydrocarbon radicals of 12 to 50 carbons, said stabilizing amount of epoxyalkyl carbamate being equal to about 0.5 to 10% by weight of the total weight of said fabric plus said epoxyalkyl carbamate, and

where radical, is derived from a fatty moiety of at least 12 carbon atoms.

4. The process of claim 3 wherein R, the hydrocarbon radical, is OH GCH wherein G is a dimerized fat radical of 14 to 48 carbon atoms.

5. The process of claim 2 wherein the epoxyalkyl carbam-ate applied to the fabric is of the structure:

can, -NHCOCH;HC-CH1 I wherein the average value of y is approximately 66.

6. The process of claim 1 wherein R is a linear polymer represented by the formula:

ENH?O-ZIC-NHE- wherein E is phenylene methylphenylene or dimethylphenylene radical and Z is selected from the group consisting of:

(a) polyalkyleneoxy -(C,,H ,,O) wherein p ranges between 3 and 6, and n is between 2 and 200 inclusive, (b) the chain of a linear polyester wherein m ranges between 2 and 10 inclusive, and v ranges between 2 and inclusive, (0) the chain OH CH=CHCH 0 wherein u ranges between 55 and 65 inclusive.

7. The process of claim 6 wherein: Z is a polyalkyleneoxy ec n oe wherein n ranges between 2 and 200 inclusive, and p ranges between 3 and 6 inclusive 8. The process of claim 6 wherein Z is the chain of a linear polyester:

wherein m ranges between 2 and 10 inclusive, and v ranges between 2 and 80 inclusive.

9. The process of claim 6 wherein Z is the polymer chain CH- 0H: CHOH hO- wherein the average value of u ranges between 55 and 65 inclusive.

11 .10., The process of claim 7 wherein the epoxyalkyl References Cited oarbamate applied to the fabric is of the structure; I UNITED STATES PATENTS F ()(.-QH2QHQ(JHQGH,O )H] i 2,830,038 4/1958 Pattison 260 775 L I 1 L i 5 3,248,373 4/1966 Barringer 260-775 CH 3,019,076 1/1962 Pardo 8-128 "E 3,279,882 10/1966 Tesqro 8-127.6 Q E v Cm 3,558,264 1/1971 Hab1b 8 127.6

0 2 10 DONALD LEVY, Primary Examiner Whemi e v ge W1 9? (#{fl between 10 and 15 H. WOLMAN, Assistant Examiner inclusive- 1 i .1 ,7 7

11. The procese of c1 aim 1 wherein the polyamine is 8 178. 117 141 tetraethylenepentamine. V 

